Processes for preparing foam composites

ABSTRACT

Processes for preparing polystyrene-phenolic foam composites and precursor compositions are described. The processes yield composites having advantageous properties useful in insulation and fire resisting applications.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of PCT/AU2014/050028, filedMay 7, 2014, which application claims priority to AU 2013 901616, filedMay 7, 2013, both of which are hereby incorporated by reference in theirentireties for all purposes.

FIELD

The present disclosure relates to processes for preparingpolystyrene-phenolic foam composites and precursor compositions. Theprocesses yield composites having advantageous properties particularly,although not exclusively, useful in insulation and fire resistingapplications.

BACKGROUND

Polystyrene foam slabs or forms are widely used for thermal and acousticinsulation in building construction. The conventional process for theproduction of a polystyrene foam slab or form is as follows:

1. Expandable polystyrene is supplied from the manufacturer inparticulate form graded for particle size. This particulate polystyrenehas a proportion of blowing agent such as pentane dissolved in it.

2. The particles are exposed to heat, usually by steam, in a fluidizedbed. As the particles pass from the bottom of the fluidized bed to thetop, they soften and as the pentane is lost from solid solution, thereleased gas causes the softened polystyrene particles to expand up tofifty times their original volume. The particles become approximatelyspherical with a very low density. The expanded polystyrene particlesare collected at the top of the bed. The particles still contain a smallamount of pentane after this primary expansion process.

3. The dry particles are introduced into moulds the walls of which arepenetrated by many small apertures. The dry particles may then becompressed. Steam is introduced into the vessel containing thepolystyrene particles. The polystyrene particles soften and the residualpentane is released. In this second stage the volume expansion of thecharge is contained by the mould walls forcing the particles togetherand fusing them to form a single, lightweight mass of expandedpolystyrene foam.

4. If the mould is in the form of a block, the blocks of expandedpolystyrene are subsequently sliced into slabs. These slices may be usedas the cores of insulating walls or panels.

A disadvantage of polystyrene foams is their high propensity to burnand/or melt in a fire leading to the loss of structural strength. Incontrast, foams with a phenolic resin matrix, that is phenolic foams, asa class of materials, are known for their excellent fire resistance andthermal properties, but their commercial potential in many fields ofapplication is impeded due to their poor structural propertiescharacterised by high brittleness and friability.

It would be desirable to identify new foam products that address theabove limitations and further desirable to employ manufacturingprocesses which utilise commonly employed process equipment such assteam block moulding.

SUMMARY

There is provided a process for preparing a particulate compositioncomprising the steps of:

-   -   a) forming a mixture of expandable thermoplastic microspheres,        reactive phenolic resole resin, and expandable polystyrene        particles, in the presence of an acidic catalyst; and    -   b) conditioning the mixture to partially cure the reactive        phenolic resole resin.

The process may comprise the steps of:

-   -   a) forming a mixture of expandable thermoplastic microspheres        and reactive phenolic resole resin, in the presence of an acidic        catalyst;    -   b) combining the mixture formed in a) with expandable        polystyrene particles to form a mixture;    -   c) conditioning the mixture formed in b) to partially cure the        reactive phenolic resole resin.

There is also provided a process for preparing a particulate compositioncomprising the steps of;

-   -   a) forming a mixture of expandable thermoplastic microspheres,        reactive phenolic resole resin, and expandable polystyrene        particles, in the presence of an acidic catalyst, and    -   b) conditioning the mixture,    -   wherein the particulate composition has a water content of less        than 10% by weight based on the total weight of the composition        and water.

There is also provided a process for preparing a particulate compositioncomprising the steps of:

-   -   a) forming a mixture of expandable thermoplastic microspheres        and reactive phenolic resole resin, in the presence of an acidic        catalyst,    -   b) combining the mixture formed in a) with expandable        polystyrene particles to form a mixture,    -   c) conditioning the mixture formed in b),    -   wherein the particulate composition has a water content of less        than 10% by weight based on the total weight of the composition        and water.

The particulate composition may comprise both a partially cured phenolicresole resin and a water content of less than 10% by weight based on thetotal weight of the composition and water.

In any of the aforementioned processes subsequent to combining thephenolic resole resin with acidic catalysts the resulting mixture may becombined with expandable polystyrene particles within 30 minutes, whensaid mixture is at a temperature of 20° C., or the mixture may becombined with expandable polystyrene particles within 15 minutes, whensaid mixture is at a temperature of 20° C., or the mixture may becombined with expandable polystyrene particles within 10 minutes, whensaid mixture is at a temperature of 20° C.

The herein disclosed processes yield particulate compositions havingexcellent handling qualities. The compositions have advantageously highflowability, enabling ease of transfer and manipulation of the particlesduring manufacturing operations.

The term partially cured as used herein means that the phenolic resoleresin may not have been subjected to temperatures above 80° C., or notabove 70° C., or the phenolic resole resin may not have been subjectedto temperatures above 80° C., or not above 70° C., for more than 1 hour,or the phenolic resole resin may not have been subjected to temperaturesabove 80° C., or not above 70° C., for more than 0.5 hour.

At least one of the constituents of the particulate compositions may beprovided in the form of an aqueous solution, dispersion or suspension.During the process of conditioning, some of the water may be removedfrom the composition, with the result that the particulate compositionbecomes substantially dry so that it is free flowing and easilytransferable. As used in this context the term ‘substantially’ meansthat the particulate composition contains less than 10% by weight waterbased on the total weight of the composition and water, or less than 7%by weight water, or less than 5% by weight water, or less than 3% byweight water, or less than 1% by weight water, or 0% water.

The processes disclosed herein may yield a partially cured phenolicresole resin that is substantially insoluble in water.

The processes disclosed, herein may comprise the optional step ofcombining a filler with one or more of the expandable thermoplasticmicrospheres, reactive phenolic resole resin or expandable polystyreneparticles or mixtures thereof prior to conditioning. The filler may beadded to the expandable thermoplastic microspheres. A range of fillersis available. One or more fillers may be used depending on thecharacteristics required of the end product. Suitable, non limitingfillers include particulate silica, talc, kaolin, clay and titaniumdioxide, glass fibre, nanocomposites or nanoparticles. Inorganiccompounds, for example particulate inorganic compounds, may be utilised.The filler may be present in amounts of 0.5-60% by weight, or 1-20% byweight, or 2-15% by weight based on the total weight of the particulatecomposition. The properties of the filler may be suitably modified bytreatment with one or more agents, for example to modify the surfaceproperties of the filler. Such treatment may, for example, reduce thesolubility of soluble fillers in a liquid, particularly an aqueousliquid. The selection of the modifying agent(s) will depend on thedesired characteristics of the filler. One class of modifying agentsincludes silanes.

The filler may have a particle size between 0.1 mm and 5 mm or theparticle size may be between 0.5 mm and 2 mm. The particulate filler maybe granular boric acid. The particle size of the granular boric acid maybe about 1 mm. The granular boric acid may be treated with a silane toyield a silane coated granular boric acid. The silane may serve toreduce the water solubility of the boric acid.

The thermoplastic microspheres may be combined with the expandablepolystyrene particles and the phenolic resole resin, optionally in thepresence of filler, and the resulting mixture treated with acidiccatalyst. The thermoplastic microspheres may first be treated withacidic catalyst and the resulting mixture combined with expandablepolystyrene particles and phenolic resole resin. Filler may then beadded to the resulting mixture. Alternatively, filler may be added atthe same time as the thermoplastic microspheres, expandable polystyreneparticles and the phenolic resole resin are being combined.

Other components may be included in the processes disclosed herein toimprove particular physical properties of the product or to reducecosts. These may be added to one or more of the expandable polystyrene,the phenolic resole resin or the thermoplastic microspheres or at anystage of mixing these components. For example, fire retardantscontaining, for example, chlorine, bromine, boron, phosphorous orammonia, especially ammonium phosphate may be added to improve fireresistance. Expandable graphite may also be usefully employed. Thegraphite may expand when exposed to high temperatures as would beencountered in a fire.

One or more surfactants may also be included in processes disclosedherein. Suitable surfactants include silicone polyethers, for examplesilicone glycol copolymers.

Water repellents, such as silicon containing aqueous emulsions may alsobe added to control or reduce water absorption.

One or more of the constituents of the processes disclosed herein may betreated with other additives and/or modifiers. For example they may betreated with a thermal conductivity modifier such as carbon,particularly an aqueous dispersed carbon. The thermoplastic microspheresmay be treated with a thermal conductivity modifier such as carbon,particularly an aqueous dispersed carbon.

There is also provided a process for preparing a particulate compositioncomprising the steps of:

-   -   a) forming a mixture of expandable thermoplastic microspheres        and acidic catalyst,    -   b) combining the mixture formed in a) with reactive phenolic        resole resin,    -   c) combining the mixture formed in b) with expandable        polystyrene particles,    -   d) conditioning the mixture formed in c) to partially cure the        reactive phenolic resole resin.

There is also provided a process for preparing a particulate compositioncomprising the steps of:

-   -   a) forming a mixture of expandable thermoplastic microspheres        and acidic catalyst,    -   b) combining the mixture formed in a) with reactive phenolic        resole resin,    -   c) combining the mixture formed in b) with expandable        polystyrene particles,    -   d) conditioning the mixture formed in c),    -   wherein the particulate composition has a water content of less        than 10% by weight based on the total weight of the composition        and water.

Optionally, one or more fillers may be added at any one or more of stepsa), b) or c). Optionally one or more additives such as surfactants orcarbon, optionally in dispersed form, may be added at any one or more ofsteps a), b) or c).

One or more steps of the processes disclosed herein may be performed inbatch or continuous modes.

Expandable Polystyrene Particles

The expandable polystyrene particles may have an average particle sizebetween 0.1 and 5 mm, or an average particle size between 0.5 and 3 mm,or an average particle size between 0.5 and 1.5 mm or an averageparticle size of between 0.7 and 1.0 mm.

The expandable polystyrene particles may contain at least one blowingagent. The polystyrene blowing agent and technique may comprise theemployment of liquid physical blowing agents, the agents which arevolatile liquids which produce a blowing gas through vaporisation of theblowing agent or through decomposition of the blowing agent when heated.

Numerous blowing agents suitable for use are well known in the art. Theblowing agent may be a liquid having an atmospheric pressure boilingpoint between −50° and 100° C., or between 0° and 50° C.

Examples of blowing agents include organic compounds such ashydrocarbons, halogenated hydrocarbons, alcohols, ketones and ethers.Specific examples of hydrocarbon blowing agents include propane, butane,pentane, isopentane and hexane. Pentane is an exemplary blowing agent.

The amount of blowing agent present in the expandable polystyreneparticles may be between 1 and 12% by weight, or between 2 and 10% orbetween 4 and 8%.

The expandable polystyrene particles may be derived from styrenepolymers that are commonly used for preparing polystyrene particles thatare to be blown to form polystyrene foam particles. As well as usingstyrene as the sole monomer other addition polymerisable monomers may beused and such copolymers are embraced by the term polystyrene in thisspecification. Styrene is always present as the major component of thepolystyrene polymer.

The expandable polystyrene particles may be unexpanded or partiallyexpanded polystyrene particles or mixtures thereof. The expandablepolystyrene particles may be partially expanded. When partially expandedpolystyrene particles are used then their density may be between 5 kg/m³to 20 kg/m³, or between 7 to 18 kg/m³, or between 9 kg/m³ to 14 kg/m³.

The expandable polystyrene particles may be modified by the addition ofone or more additives, such as flame retardants, smoke suppressants,antistatic agents, flowability improvers, foaming modifiers, and otheradditives commonly found or used in expandable polystyrene particles.For example, the expandable polystyrene particles may be coated orimpregnated with carbon or graphite.

Reactive Phenolic Resole Resin

Base-catalysed phenol-formaldehyde resins made with a formaldehyde tophenol ratio of greater than one (usually around 1.5) may be termedresoles. A suitable reactive phenolic resole resin as used herein mayhave a viscosity of between 500-4,000 cP at a temperature of 25° C., ora viscosity of between 1000-3000 cP at a temperature of 25° C. Thereactive phenolic resole resin as used herein may have a water contentof 2-7% by weight based on the total weight of the reactive phenolicresole resin and water, or a water content of 3-6% by weight based onthe total weight of the reactive phenolic resole resin and water. Thereactive phenolic resole resin as used herein may have a free phenolcontent of less than 25% by weight relative to the total weight of thereactive phenolic resole resin and water, or less than 20% by weight, orless than 18% by weight. The free phenol content may be between 10% and20% by weight, or may between 14% and 18% by weight. The reactivephenolic resole resin as used herein may have a free formaldehydecontent of less than 3% by weight, or a free formaldehyde content ofless than 1% by weight relative to the total weight of the reactivephenolic resole resin and water. The reactive phenolic resole resin mayhave a pH of 7 or less, or a pH of 6.6 or less. The reactive phenolicresole resin may have any one or any combination of the above disclosedfeatures.

Expandable Thermoplastic Microspheres

The expandable thermoplastic microspheres as used herein may have anaverage particle size from between 1 and 100 microns, or an averageparticle size from between 2 and 50 microns, or an average particle sizefrom between 5 and 20 microns. The expandable thermoplastic microspheresmay be derived from unexpanded or partially expanded microspheres or amixture thereof, and comprise a thermoplastic polymer shell made of ahomopolymer or copolymer. Mixtures of different thermoplasticmicrospheres may be utilised.

The thermoplastic polymer shell of the thermoplastic microspheres may bederived from monomers selected from the group consisting ofacrylonitrile, methacrylonitrile, α-chloroacrylonitrile,α-ethoxyacrylonitrile, fumaroacryfonitrile, crotoacrylonitrile, acrylicesters, methacrylic esters, vinyl chloride, vinylidene chloride,vinylidene dichloride, vinyl pyridine, vinyl esters, and derivatives ormixtures thereof.

The thermoplastic polymer shell may be derived from vinylidene chloridemonomer.

The expandable thermoplastic microspheres may contain a propellantencapsulated within the thermoplastic polymer shell. The microspheresmay expand by heating above the boiling point of the propellant andabove the softening point of the polymer shell.

The propellant may be a volatile liquid trapped within the polymershell. Suitable propellants include various short chain alkanes andshort chain isoalkanes such as, but not limited to, isopentane,isobutane, n-butane, hexane, heptane, isooctane, petroleum ether andpentane or mixtures thereof.

Suitable thermoplastic microspheres may begin to soften in thetemperature range 70-100° C., or 85-95° C. Maximum expansion may occurin the temperature range of 100-150° C., or 115-125° C.,

The expandable thermoplastic microspheres may be provided in the form ofan aqueous dispersion. The amount of expandable microspheres in theaqueous dispersion may be between 2 and 60% by weight based on the totalweight of the aqueous dispersion, or between 5 and 40% by weight basedon the total weight of the dispersion, or between 10 and 25% by weightbased on the total weight of the dispersion.

The expandable microspheres may be combined with one or more fillersprior to mixing with the other components of the particulatecomposition. An aqueous dispersion of expandable microspheres may betreated with the particulate filter. If required, the filler may bepre-treated with a suitable modifying agent.

Acidic Catalyst

The acidic catalyst as used herein may be a strong inorganic or organicacid or their esters. Strong organic acids include sulphonic acids andtheir esters including benzene sulphonic acid, toluene sulphonic acid,phenol sulphonic acid, xylene sulphonic acid, β-naphthalene sulphonicacid, α-naphthalene sulphonic acid, esters thereof and mixtures thereof.The acids may further include weak inorganic acids and their esters,either alone or in admixture. The acids that may be employed stillfurther include mixtures of two or more of strong organic acids,mixtures of two or more of esters of strong organic acids, mixtures oftwo or more of weak inorganic acids, or mixtures of two or more ofesters of weak inorganic acids, as well as mixtures of different acidsor their esters. Suitable catalysts are phosphate esters and blends ofphosphoric acid with strong organic acids such as para-toluene sulphonicacid or any other sulphonic acid or its ester. Mixtures of any two ormore of the acids and/or esters may also be used.

The particulate compositions prepared according to the processesdisclosed herein comprise a reactive phenolic resole resin that may becured and may be considered as precursor compositions topolystyrene-phenolic foam composites.

Accordingly, there is provided a process for preparing apolystyrene-phenolic foam composite comprising the steps of:

-   -   a) forming a mixture of expandable thermoplastic microspheres,        reactive phenolic resole resin and expandable polystyrene        particles in the presence of an acidic catalyst,    -   b) conditioning the mixture to partially cure the reactive        phenolic resole resin, and    -   c) further curing the conditioned mixture with steam to form the        composite.

There is also provided a process for preparing a polystyrene-phenolicfoam composite comprising the steps of:

-   -   a) forming a mixture of expandable thermoplastic microspheres        and reactive phenolic resole resin in the presence of an acidic        catalyst;    -   b) combining the mixture formed in a) with expandable        polystyrene particles to form a mixture;    -   c) conditioning the mixture formed in b) to partially cure the        reactive phenolic resole resin; and    -   d) further curing the conditioned mixture with steam to form the        composite.

There is also provided a process for preparing a polystyrene-phenolicfoam composite comprising the steps of:

-   -   a) forming a mixture of expandable thermoplastic microspheres,        reactive phenolic resole resin and expandable polystyrene        particles in the presence of an acidic catalyst;    -   b) conditioning the mixture to provide a water content of less        than 10% by weight based on the total weight of the mixture and        water; and    -   c) further curing the conditioned mixture with steam to form the        composite.

There is also provided a process for preparing a polystyrene-phenolicfoam composite comprising the steps of:

-   -   a) forming a mixture of expandable thermoplastic microspheres        and reactive phenolic resole resin in the presence of an acidic        catalyst;    -   b) combining the mixture formed in a) with expandable        polystyrene particles to form a mixture;    -   c) conditioning the mixture formed in b) to provide a water        content of less than 10% by weight based on the total weight of        the conditioned mixture and water; and    -   d) further curing the conditioned mixture with steam to form the        composite.

There is also provided a process for preparing a polystyrene-phenolicfoam composite comprising the steps of:

-   -   a) forming a mixture of expandable thermoplastic microspheres        and acidic catalyst;    -   b) combining the mixture formed in a) with reactive phenolic        resole resin;    -   c) combining the mixture formed in b) with expandable        polystyrene particles;    -   d) conditioning the mixture formed in c) to partially cure the        reactive phenolic resole resin; and    -   e) further curing the conditioned mixture with steam to form the        composite.

There is also provided a process for preparing a polystyrene-phenolicfoam composite comprising the steps of

-   -   a) forming a mixture of expandable thermoplastic microspheres        and acidic catalyst;    -   b) combining the mixture formed in a) with reactive phenolic        resole resin;    -   c) combining the mixture formed in b) with expandable        polystyrene particles;    -   d) conditioning the mixture formed in c) to provide a water        content of less than 10% by weight based on the total weight of        the conditioned mixture and water; and    -   e) further curing the conditioned mixture with steam to form the        composite.

Optionally, one or more fillers may be added at any one or more of stepsa), b) or c). Optionally one or more additives such as surfactants orcarbon, optionally in dispersed form, may be added at any one or more ofsteps a), b) or c).

The conditioned mixture according to any of the aforementionedembodiments may have a water content of less that 10% by weight based onthe total weight of the composition and water, or a water content ofless that 7% by weight based on the total weight of the composition andwater, or a water content of less that 5% by weight based on the totalweight of the composition and water, or a water content of less that 3%by weight based on the total weight of the composition and water.

In any of the herein disclosed curing processes, after conditioning thecompositions may be held for a period of time from between 1 hour and 72hours prior to curing, or from between 2 hours and 48 hours, or frombetween 4 hours and 48 hours. After conditioning the compositions may beheld for any of these time periods at a temperature of no more than 30°C. or no more than 25° C. or no more than 20° C.

The polystyrene-phenolic foam composites produced from the processesdisclosed herein may be characterised by having expanded polystyreneand/or the expanded thermoplastic microspheres, at least in part,solubilised in a cured phenolic resin.

Advantageously, the further curing step may be suitably performed in asteam block moulder which is typically utilised in the polystyreneindustry for the manufacture of polystyrene blocks. This provides asignificant cost advantage due to the very short processing timesrequired. Therefore total batch cycle time may be reduced.

Further, energy savings of about 30% may be realised in comparison topreparing a traditional expanded polystyrene block in a steam blockmoulder.

The steam expansion process is also advantageous in comparison tocompression moulding processes.

The further curing step may be performed in a sheet moulding machine soas to produce one or more sheets. The further curing step may also beperformed in a continuous panel press to produce, for example, panels orsheets in a continuous fashion.

One or more steps of the processes disclosed herein may be performed inbatch or continuous modes.

It is surprising that the phenolic resin, a condensation polymer, may becured with steam, which intuitively may be considered to inhibit thereaction. However, without wishing to be bound by theory, the presentdisclosure demonstrates that, provided the phenolic resin is at leastpartially cured, further curing with steam may be effective.

The processes disclosed herein may utilise expandable polystyrene,thermoplastic microspheres, phenolic resole resin, fillers, treatedfillers, and other components as hereinbefore disclosed.

The processes may utilise from 20 to 80 wt. % of expandable polystyreneparticles, from 20 to 60 wt. % of reactive phenolic resole resin andfrom 0.5 to 5 wt. % of thermoplastic microspheres based on the totalweight of these three components, or from 35 to 65 wt. % of expandablepolystyrene particles, from 25 to 50 wt. % of reactive phenolic resoleresin and from 1.5 to 5 wt. % of thermoplastic microspheres based on thetotal weight of these three components.

Conditioning and Curing Processes

Conditioning the mixture is a key feature of the processes. Theconditioning may be performed at a temperature from between 5° C. and80° C., or between 20° C. and 80° C., or between 50° C. and 70° C. Thetime for conditioning may be between 0.25 hr and 10 hr, or between 0.25hr and 5 hr, or between 0.25 hr and 2 hr. Conditioning in this wayeffectively amounts to ‘B staging’, a term commonly used in the art todescribe the removal of solvent, in this case water, from a resin, withonly partial curing occurring. It is important that the mixture afterconditioning is substantially touch dry, yet has only achieved a partialdegree of cure. An important characteristic of the product afterconditioning is that it is substantially flowable.

On curing the phenolic resole resin, which must be highly reactive asherein described, it may bind and/or solubilise the polystyreneparticles and/or the thermoplastic microparticles, as well as any otherbeneficial functional additives present.

Suitable thermoplastic microspheres may begin to soften in thetemperature range of 70-100° C., or 85-95° C. and maximum expansion mayoccur in the range of 100-150° C., or 115-125° C. However, in thepresence of phenolic resole resin, the shells may be plasticised andpartially solubilised so that expansion may begin in the range of 50-70°C., or 55-60° C.

When steam is introduced into the mixture the polystyrene particlessoften and expand due to an increase in the blowing agent vapourpressure. Steam exposure may also soften the phenolic resin. Thethermoplastic microspheres may also readily expand with heat whenplasticised by the phenolic resin. The result of this may be to minimisethe interstitial volume of the composite and to substantially fuse thepolystyrene particles and phenolic foam together into a solid foam. Anadvantage of the processes disclosed herein is that the resultingcomposites may be produced quickly and efficiently using standardexpanded polystyrene processing equipment. The steam curing step maytake from 1 minute to 60 minutes, or from 1 minute to 30 minutes, orfrom 1 minute to 15 minutes. Advantageously, a combination of steam andvacuum may be used so as to control the pressure within the curing unit.The temperature of the steam may be in the range of 105 to 110° C.

A feature of curing is the mechanism by which the highly reactivephenolic resole resin may plasticise and interact physically and/orchemically with the thermoplastic shell of the microspheres and/or withthe polystyrene. After processing, the phenolic resin may solubilise,and/or mix and/or cross-link with the thermoplastichomopolymer/copolymer and/or polystyrene and, as a result; a compositeproduct may be formed whereby the phenolic resin modified microspheresand/or polystyrene become highly fire resistant and the phenolic foam soformed is no longer rigid and brittle but is, conversely, tough andresilient in nature.

Properties of the Foam Composites

A feature of the composites is the plasticisation and physical and/orchemical interaction of the cured phenolic resole resin with thethermoplastic shell of the microspheres and/or with the polystyreneparticles. The phenolic resin may solubilise, and/or mix, and/orcross-link with the thermoplastic homopolymer/copolymer of themicrospheres and/or polystyrene particles and, as a result, a compositeproduct is formed. When the composite is exposed to a heat source itadvantageously maintains its structural integrity.

The solubilisation and/or mixing and/or chemical interaction may accountfor, at least in part, the low interstitial volume and low waterabsorption of the foam composites.

Where physical interaction occurs this may be in the form of polymerentanglement which may form an interpenetrating polymer network.

The foam composites prepared by the processes disclosed herein may besemi-resilient and non-friable compared to other structural foams.Densities may be produced in the range 10-50 kg/m3, or 10-40 kg/m³, or10-30 kg/m° depending on formulation and additives. Despite theapparently flammable thermoplastic microsphere and polystyrene content,the foam composites are highly resistant to temperature and fire, likelydue to the solubilisation of the polymer shell of the microspheresand/or the polystyrene by the phenolic resin. Desirable flame stabilityis also observed whereas conventional phenolic foams and resin are oftensubject to spalling/punking. The foam composites possess excellentphysical and chemical properties. The cured phenolic resole resin is notrigid and brittle but is, conversely, tough and resilient in nature.

The foam composites prepared according to the processes disclosed hereinmay have a specific mass loss rate @ 50 kW, measured according to ISO17554, of less than 8 g/m²·s, or less than 6 g/m²·s, or less than 4g/m²·s, or less than 2 g/m²·s.

The foam composites prepared according to the processes disclosed hereinmay exhibit insulation failure times, according to AS1530.4, for a 100mm thick panel, of greater than 30 minutes, or greater than 20 minutes,or greater than 10 minutes. The foam composites prepared by theprocesses disclosed herein advantageously may possess low interstitialvolume. While not wishing to be bound by theory it is believed thatduring steam curing solubilisation of the polystyrene and/orthermoplastic microsphere phases in the phenolic phase occurs, and thisaccounts, at least in part, for the low interstitial volume. Theinterstitial volume may be 5% or less, or 3% or less, or 1% or less, or0.5% or less, or 0.3% or less.

The foam composites prepared by the disclosed processes advantageouslymay possess low water absorption in accordance with ASTM C272 (StandardTest Method for Water Absorption of Core Materials for SandwichConstructions). The water absorption of the foam composites may be 8% byvolume or less, or 7% by volume or less, or 5% by volume or less, orbetween 4 and 8% by volume, or between 5 and 7% by volume.

There is also provided a foam composite prepared according to any one orthe processes as herein disclosed.

There is also provided a composite block comprising the foam compositeprepared according to any one of the processes as herein disclosed.

There is also provided a panel or a sheet comprising the foam compositeprepared according to any one of the processes as herein disclosed.

The blocks, panels and/or sheets find advantageous use in applicationsrequiring thermal and/or acoustic insulation, for example, inconstruction.

There is also provided a construction material comprising the blocks,panels and/or sheets as hereinbefore disclosed.

Throughout this specification, use of the terms “comprises” or“comprising” or grammatical variations thereon shall be taken to specifythe presence of stated features, integers, steps or components but doesnot preclude the presence or addition of one or more other features,integers, steps, components or groups thereof not specificallymentioned.

For the sake of brevity, only certain ranges are explicitly disclosedherein. However, ranges from any lower limit may be combined with anyupper limit to recite a range not explicitly recited, as well as, rangesfrom any lower limit may be combined with any other lower limit torecite a range not explicitly recited, in the same way, ranges from anyupper limit may be combined with any other upper limit to recite a rangenot explicitly recited.

DETAILED DESCRIPTION

It will now be convenient to describe the disclosure with reference toparticular embodiments and examples. These embodiments and examples areillustrative only and should not be construed as limiting upon the scopeof the disclosure. It will be understood that variations upon thedescribed disclosure as would be apparent to the skilled addressee arewithin the scope of the disclosure. Similarly, the present disclosure iscapable of finding application in areas that are not explicitly recitedin this document and the fact that some applications are notspecifically described should not be considered as a limitation on theoverall applicability of the disclosure.

Thermoplastic Microspheres

When thermoplastic microspheres are heated, the polymeric shellgradually softens, and the liquid within the shell begins to gasify andexpand. When the heat is removed, the shell stiffens and the microsphereremains in its expanded form. When fully expanded, the volume of themicrospheres may increase more than 40 times. Significant densityreductions can be achieved with even a small concentration of, forexample, 3% thermoplastic microspheres by weight. A benefit of thehollow microsphere is the potential to reduce part weight, which is afunction of density. Compared to traditional mineral-based additives,such as calcium carbonate, gypsum, mica, silica and talc, hollowmicrospheres have much lower densities. Loadings may be 1-5% by weight,which can equate to 25% or more by volume.

The expandable thermoplastic microspheres suitable for preparing theparticulate compositions and foam composites as disclosed herein, may beutilised in various forms. They may be in the form of a slurry dispersedin water or they may be utilised in dry form. Aqueous dispersions arepreferred. Suitable microspheres are supplied by AkzoNobel under thetrade mark Expancel®.

Reactive Phenolic Resole Resin

A reactive phenolic resole resin suitable for further curing, that is,to form a partially cured (‘B staged’) or substantially completely curedresin, may be produced by the base-catalysed condensation reaction of amolar excess of an aldehyde, with a substituted or unsubstituted phenol.Preferred substituted phenols are those in which the substituent doesnot impede the condensation of the phenol(s) with the aldehyde(s).Suitable substituents include halogens or a hydroxy, alkyl or an arylgroup. Unsubstituted phenol is most preferred. Suitable aldehydes areformaldehyde (including oligomers/polymers such as trioxane), furfural,sugars and cellulose hydrolysates. A preferred aldehyde is formaldehyde.In one embodiment the molar ratio of aldehyde to phenol is from 1.4 to1.8:1, for example, about 1.6:1. The temperature at which the phenolicresole resin is prepared may be less than 65° C., for example no morethan 60° C.±2° C., or no more than about 60° C. This temperature of lessthan 65° C. is preferably maintained while the basic catalyst is active,that is, until the basic catalyst is neutralised. This temperature mayallow the maximum substitution of the phenol aromatic ring by reactivemethylol (—CH₂OH) groups and results in only low molecular weightdevelopment in the polymer. Water may then be optionally distilled offto the preferred specification. Due to the resulting low molecularweight (preferably less than 1000 Daltons), the phenolic resole resin ishighly soluble in water without phase separation and remainssufficiently reactive to cross-link under dilute aqueous conditions.

Suitable alkaline condensation catalysts are ammonia, ammoniumhydroxide, sodium hydroxide, potassium hydroxide and barium hydroxide.Sodium hydroxide is a preferred catalyst.

The phenolic resole resin may be produced from phenol with a molarexcess of formaldehyde in the presence of sodium hydroxide as acondensation catalyst.

Conventional phenolic resins may be produced by carefully increasing thetemperature to around 60±2° C. and holding there for a period of about 1hour, after which the temperature is increased to around 80° C. for afurther period of 2-4 hours. The two stages essentially are:

1. Ring Substitution at 60° C. by formaldehyde into the phenol aromaticring; and

2. Condensation Polymerisation at 80° C. to increase molecular weight.

In contrast, the reactive phenolic resole resin as used herein may beobtained, for example, by only heating to no more than 65° C., forexample, no more than 60±2° C. or no more than about 60° C. for a periodof about 5 hours or until an intermediate viscosity of 13.5-14.5centiStokes at 25° C. is reached for the reaction mixture. This leads tomaximum substitution by methylol (—CH₂OH) groups in ortho-, meta- andpara-positions of the aromatic ring and only low molecular weight build.The mixture may then be neutralised with an acid such as para-toluenesulphonic acid to a pH of less than 7, or between 5.5-6.6, or about 6and most of the process and reaction water may then be distilled offunder vacuum down to a level of around 2-7%, resulting in a highlyreactive material.

Fillers

The particulate composition and/or the phenolic composites may compriseone or more fillers. Suitable, non limiting fillers include inorganiccompounds, particularly particulate inorganic compounds.

Exemplary fillers include elemental metal selected from the groupconsisting of metals of Groups I, II, III and IV, transition metals orthe like of the periodic table, oxides or complex oxides of thesemetals, salts of these metals, such as fluorides, carbonates, sulfates,silicates, hydroxides, chlorides, sulfites, and phosphates of thesemetals, and composites of these salts of metals. Preferably used aremetal oxides such as amorphous silica, quartz, alumina, titania,zirconia, barium oxide, yttrium oxide, lanthanum oxide, and ytterbiumoxide, silica-based complex oxides such as silica-zirconia,silica-titania, silica-titania-barium oxide, andsilica-titania-zirconia, glass such as borosilicate glass, glass fibres,aluminosilicate glass, or fluoroaluminosilicate glass, metal fluoridessuch as barium fluoride, strontium fluoride, yttrium fluoride, lanthanumfluoride, and ytterbium fluoride; inorganic carbonates such as calciumcarbonate, magnesium carbonate, strontium carbonate, and bariumcarbonate; and metal sulfates such as magnesium sulfate and bariumsulfate. Other suitable fillers include particulate silica, talc,kaolin, clay, nanocomposites and nanoparticles. Other inorganiccompounds such as boric acid may be utilised as a filler.

The filler may be present in amounts of 0.5-60% by weight, or 1-20% byweight or 2-15% by weight, based on the total weight of the particulatecomposition or composite.

The filler may have a particle size between 0.1 mm and 5 mm, or between0.5 mm and 2 mm. One preferred particulate filler is granular boricacid. Granular boric acids of particle size of about 1 mm may besuitable.

Modified Filters

Often it is advantageous to treat fillers with a modifying agent so asto modify the surface properties of the filler. For example fillers maybe modified with agents so as to change the fillers solubilityproperties. Suitable modifying agents are well known in the art. Oneclass of modifying agents are silanes. One class of silanes arehaloalkylsilanes examples of which are 3-chloropropyltrimethoxysilane,3-chloropropyltriethoxysilane, 3-chloropropyltripropoxysilane,chloropropylmethyldimethoxysilane, chloropropylmethyldiethoxysilane,chloropropyldimethylethoxysilane, chloropropyldimethylmethoxysilane,chloroethyltrimethoxysilane, chloroethyltriethoxy-silane,chloroethylmethyldimethoxysilane, chloroethylmethyldiethoxysilane,chloroethyldimethylmethoxysilane, chloroethyldimethylethoxysilane,chloromethyltriethoxy-silane, chloromethyltrimethoxysilane,chloromethylmethyl-dimethoxysilane, chloromethylmethyldiethoxysilane,chloro-methyldimethylmethoxysilane or chloromethyldimethylethoxysilane.

Granular boric acid may be treated with one or more of the above silanesso as to reduce the solubility of the boric acid in water.

Materials and Process

In an exemplary embodiment a preblend of the following components asdescribed herein may be prepared. After combining the components thepreblend may be stored for future use. The specific gravity of themixture may be in the range 1.4 to 1.7. Continuous slow agitation duringthe manufacturing process may be utilised.

Preblend %. w/w Expandable thermoplastic microspheres 9.3% Boric acid56.0% Carbon dispersion 15.6% Surfactant 0.4% Acidic catalyst 18.7%

The preblend may be combined with reactive phenolic resole to form areactive liquid matrix in the exemplary proportions shown below. Thisliquid matrix may have a shelf life of between 4 and 10 minutes at about20° C. after which time exothermic cross linking may occur. The rate ofcross linking is temperature dependent.

Liquid matrix %. w/w Reactive phenolic resole 76% Preblend 24%

The liquid matrix may be used to coat partially expanded polystyreneparticles in the exemplary proportions (and exemplary ranges) shownbelow.

Foam composite %. w/w Partially expanded polystyrene 45% (25% to 65%)Liquid Matrix 55% (35% to 70%)

Coating

Coating may be performed in a batch mixer such as a ribbon type mixer.The components may also be blended in a continuous process by preparingthe liquid matrix immediately prior to coating partially expandedpolystyrene particles.

A stream of partially expanded polystyrene particles may be introducedinto, for example, a rotating drum beneath liquid matrix feed streamssuch that the liquid matrix is drizzled over the surface of the movingpartially expanded polystyrene particles. Rotation of the drum mayfacilitate even distribution of the matrix evenly over the surfaces ofthe partially expanded polystyrene particles.

The absence of any form of strakes or mixing impellors in the rotatingdrum may advantageously eliminate the matrix coming into contact withother surfaces, and potential adherence to parts of the mixer.

Conditioning (B-Staging) to Form Particulate Composition

Conditioning may conveniently be performed in, for example, a rotatingdrum. Air heated to between, for example, 45° C. and 60° C. may bepassed through the drum and the coating material may progressively losefree water and may initiate cross linking and bond development betweenthe partially expanded polystyrene and the matrix.

During the conditioning process the product characteristic may changefrom a wet free flowing high viscosity fluid to a sticky plastic, andfinally to discrete clumps of lightly adhering mixture.

Coated product exiting the drum may drop on to a mesh conveyor belt ortray. The belt may be fully enclosed in a heated chamber with suitablemeans of passing air heated to between, for example, 45° C. and 60° C.over the coated product. The size and speed of the belt or tray may besuch that the coated product remains as an undisturbed 100 mm thicklayer for about 45 mins duration.

Discharge off the belt into a grizzly feeder or combination ofgranulator and sizing mesh may be required to break down the aggregatedmaterial into discrete coated grains ready for conveying into storageprior to composite formation.

Composite Formation

Clamshell style vacuum assisted expanded polystyrene block mouldingequipment may be suitable for processing the coated product into blocks.Coated product may be allowed to come to equilibrium in a fully ventedstorage space where the temperature preferably does not exceed 20° C.for between 4 hrs and 48 hrs from coating. Air transport may be used toconvey material to standard block moulder filling guns via a de-dustingstation to remove any fines generated during the coated product handlingprocesses.

A standard expandable polystyrene block making cycle may be employedwith maximum steam pressure being for example about 2 bar and utilisinggentle cross steaming with vacuum assistance. Polishing of mouldsurfaces may be utilised so as to minimise mechanical keying of thematrix to the mould surface thereby facilitating clean ejection of thefinished block.

Fire Resistance Testing

Fire resistance may be tested in terms of integrity and insulation.

Integrity

Integrity may be defined as the ability of an element of construction toresist the passage of flames and hot gases from one space to anotherwhen tested in accordance with AS1530.4. Failure for integrity criteriais deemed to occur when continuous flaming occurs on the non-exposedside of the test specimen, or when cracks, fissures and other openingsthrough which hot flames and gases can pass through are present.

Insulation

Insulation may be defined as the ability of an element of constructionto maintain a temperature on the surface that is not exposed to a heatsource, below the limits specified, when tested in accordance withAustralian. Standard AS1530.4 (Fire Resistance Test to BuildingMaterial). Failure for insulation criteria is deemed to have occurredwhen the temperature rise of the non exposed side exceeds predeterminedthresholds.

Panels manufactured from composites prepared according to the presentdisclosure achieve 30 mins insulation for 100 mm thick panels whentested according to AS1530.4.

EXAMPLES

The following example utilised the components as set out in Table 1. Theweights of the thermoplastic microspheres and the carbon dispersioninclude water present in the materials.

Example 1

TABLE 1 Material % w/w Expanded polystyrene 69.7 (Lambdapor 753p)Phenolic resole resin 23.2 Thermoplastic 1.74 microspheres (Expancel ®820 SLU40) Treated boric acid 3.48 Aqueous carbon 0.46 dispersionCatalyst (p-toluene 1.39 sulphonic acid)

Preparation of Microsphere Composition

Particulate boric acid was treated with 3-chloropropyltrimethoxysilanefollowed by heating the mixture to 70° C. for 30 mins.

A microsphere composition comprising expandable thermoplasticmicrospheres, coated boric acid, carbon dispersion and catalyst wasprepared by mixing the components in a plough-share mixer for 5 mins.The resultant blend was then sieved through a vacuum assisted Buchnerfunnel fitted with 1 mm aperture square mesh.

Preparation of the Particulate Composition

Polystyrene was expanded to a density of 18 kg/m³ and retained in a silofor 11 hrs. The partially expanded polystyrene was fed into a mixinghead at a rate of 68 litres/min. The phenolic resole resin was pumpedinto the mixing head at a rate of 0.68 kg/min. The microspherecomposition was pumped into the mixing head at a rate of 0.208 kg/min.

A multi stream nozzle fed a curtain of phenolic resin and microspherecomposition over the moving polystyrene particles in a mixer at atemperature between 15° C. and 30° C.

After approximately 3 minutes the resultant mixture was fed into asecond rotating drum with a hot air curtain blowing over the mix. Theair temperature was maintained between 50° C. and 75° C. with a transittime of 10 mins.

The discharge was transferred to a fluid bed and held at 35° C. for upto 45 minutes. This material was then fed via air transport to a clothsilo, where it was held for 24 hours.

Preparation of Polystyrene/Phenolic Composite

The material was then removed from the silo by suction and blown into ablock moulder silo and drained down to fill a block mould. Once themould was filled, a steam cycle was commenced which yielded thecompleted composite within 10 mins.

Example 2 Preparation of Microsphere Composition

Particulate boric acid was treated with 3-chloropropyltrimethoxysilanefollowed by heating the mixture to 70° C. for 30 mins.

A microsphere composition comprising expandable thermoplasticmicrospheres, coated boric acid, and carbon dispersion was prepared bymixing the components in a plough-share mixer for 5 mins. The resultantblend was then sieved through a vacuum assisted Buchner funnel fittedwith 1 mm aperture square mesh.

Preparation of the Particulate Composition

Polystyrene was expanded to a density of 18 kg/m³ and retained in a silofor 11 hrs. The partially expanded polystyrene was fed into a mixinghead at a rate of 68 litres/min. The phenolic resole resin was pumpedinto the mixing head at a rate of 0.68 kg/min. The microspherecomposition was pumped into the mixing head at a rate of 0.167 kg/min.

A multi stream nozzle fed a curtain of phenolic resin and microspherecomposition over the moving polystyrene particles in a mixer at atemperature between 15° C. and 30° C. Catalyst was added to the mixtureat the mixer discharge at a rate of 0.0488 kg/min.

After approximately 3 minutes the resultant mixture was fed into asecond rotating drum with a hot air curtain blowing over the mix. Theair temperature was maintained between 50° C. and 75° C. with a transittime of 10 mins.

The discharge was transferred to a fluid bed and held at 35° C. for upto 45 minutes. This material was then fed via air transport to a clothsilo, where it was held for 24 hours.

Preparation of Polystyrene/Phenolic Composite

The material was then removed from the silo by suction and blown into ablock moulder silo and drained down to fill a block mould. Once themould was filled, a steam cycle was commenced which yielded thecompleted composite within 10 mins.

In an alternate experiment the material from the silo was used to fillmultiple sheet moulds and the moulds were subsequently steamed for 10mins to produce completed sheets.

Example 3 Preparation of Microsphere Composition

Particulate boric acid was treated with 3-chloropropyltrimethoxysilanefollowed by heating the mixture to 70° C. for 30 mins. The material wassieved and the fraction retained on BS#10 mesh discarded.

A microsphere composition comprising expandable thermoplasticmicrospheres, carbon dispersion and catalyst was prepared by mixing thecomponents in a plough-share mixer for 5 mins.

Preparation of the Particulate Composition

Polystyrene was expanded to a density of 18 kg/m³ and retained in a silofor 11 hrs. The partially expanded polystyrene was fed into a mixinghead at a rate of 68 litres/min. The phenolic resole resin was pumpedinto the mixing head at a rate of 0.68 kg/min. The microspherecomposition was pumped into the mixing head at a rate of 0.105 kg/min.The treated boric acid was fed into the mixing head at a rate of 0.102kg/min.

A multi stream nozzle fed a curtain of phenolic resin and microspherecomposition over the moving polystyrene particles in a mixer at atemperature between 15° C. and 30° C.

After approximately 3 minutes the resultant mixture was fed into asecond rotating drum with a hot air curtain blowing over the mix. Theair temperature was maintained between 50° C. and 75° C. with a transittime of 10 mins.

The discharge was transferred to a fluid bed and held at 35° C. for upto 45 minutes. This material was then fed via air transport to a clothsilo, where it was held for 24 hours.

Preparation of Polystyrene/Phenolic Composite

The material was then removed from the silo by suction and blown into ablock moulder silo and drained down to fill a block mould. Once themould was filled, a steam cycle was commenced which yielded thecompleted composite within 10 mins.

In an alternate experiment the material from the silo was used to fillmultiple sheet moulds and the moulds were subsequently steamed for 10mins to produce completed sheets.

Example 4 Preparation of Microsphere Composition

Particulate boric acid was treated with 3-chloropropyltrimethoxysilanefollowed by heating the mixture to 70° C. for 30 mins. The material wassieved and the fraction retained on BS#10 mesh discarded.

A microsphere composition comprising expandable thermoplasticmicrospheres, carbon dispersion and catalyst was prepared by mixing thecomponents in a plough-share mixer for 5 mins.

Preparation of the Particulate Composition

Polystyrene was expanded to a density of 18 kg/m³ and retained in a silofor 11 hrs. The partially expanded polystyrene was fed into a mixinghead at a rate of 68 litres/min. The phenolic resole resin was pumpedinto the mixing head at a rate of 0.68 kg/min. The microspherecomposition was pumped into the mixing head at a rate of 0.105 kg/min.The treated boric acid was fed into the mixing head at a rate of 0.102kg/min.

A multi stream nozzle fed a curtain of phenolic resin and microspherecomposition over the moving polystyrene particles in a mixer at atemperature between 15° C. and 30° C.

After approximately 3 minutes the resultant mixture was fed into asecond rotating drum with a hot air curtain blowing over the mix. Theair temperature was maintained between 50° C. and 75° C. with a transittime of 10 mins.

The discharge was transferred to a fluid bed and held at 35° C. for upto 45 minutes. This material was then fed via air transport to a clothsilo, where it was held for 24 hours.

Preparation of Polystyrene/Phenolic Composite

The material was then removed from the silo by suction and blown into acontinuous tractor type moving belt panel press with our without usingfacing steel sheets on two faces. The material in the press was steamedas it progressed through the press to form completed sheets or completedinsulated panel sith steel, aluminium or other material facings. Thecontinuous press was moving a between 1 and 15 metres/min.

Table 2 indicates the formulations of other composites prepared in asimilar manner to Example 1 above.

TABLE 2 Run no. 1 2 3 4 5 6 7 Expanded Polystyrene 38.7 52.5 64.8 58.452.3 53.5 52.6 %(w/w) Phenolic Resin 47.0 36.4 27.0 31.9 35.8 36.6 36.0%(w/w) Thermoplastic 3.5 2.7 2.0 2.4 3.6 1.5 2.7 Microspheres %(w/w)Treated Boric Acid 7.0 5.5 4.0 4.8 5.4 5.5 5.4 %(w/w) Carbon Dispersion0.9 0.7 0.5 0.6 0.7 0.7 0.7 %(w/w) Catalyst 2.8 2.2 1.6 1.9 2.2 2.2 2.2% (w/w)

It was found that all of the composites had excellent physicalproperties (low interstitial volume and low water absorptiondemonstrating advantage over a wide range of relative component amounts.The mechanical properties of the composites were equivalent to expandedpolystyrene.

Fire Resistance Testing

Test specimens consisted of insulated wall panels comprising foamcomposites as prepared by the processes disclosed herein. The panelswere 3.0 m high, 1.2 m or 0.6 m broad and had a thickness of 50 mm, 100mm and 250 mm. A comparative test was performed with a 125 mm thickexpanded polystyrene panel. Tests were conducted in accordance with AS1530.4 ‘Methods for fire tests on building materials, components andstructures, Part 4: Fire resistance tests of elements of construction.Section 3 Walls—Vertical Separating Elements’. The results are collectedin Table 3.

TABLE 3 Insulation failure time Material and thickness (minutes)Inventive composite 50 mm 15 Inventive composite 100 mm 31 Inventivecomposite 250 mm 115 Comparative Polystyrene 125 mm 6

It is clear from the results that the composites prepared by theprocesses disclosed herein significantly outperform expanded polystyrenein fire resistance.

Tests were also conducted following ISO 17554. This is a small-scalemethod for assessing the mass loss rate of essentially flat specimensexposed in the horizontal orientation to controlled levels of radiantheating with an external igniter under well-ventilated conditions. Themass loss rate is determined by measurement of the specimen mass and isderived numerically. Mass loss rate can be used as an indirect measureof heat release rate.

Under the conditions of the test expanded polystyrene had an averagespecific mass loss rate @ 50 kW, over three tests, of 9.81 g/m²·s,whereas composites prepared by the processes disclosed herein had anaverage specific mass loss rate @ 50 kW, over three tests, of 1.27g/m²·s. Accordingly, significantly slower combustion was observed withthe inventive composites.

1. A process for preparing a particulate composition comprising thesteps of: a) forming a mixture of expandable thermoplastic microspheres,reactive phenolic resole resin and expandable polystyrene particles inthe presence of an acidic catalyst; and b) conditioning the mixture topartially cure the reactive phenolic resole resin.
 2. A processaccording to claim 1 comprising the steps of: a) forming a mixture ofexpandable thermoplastic microspheres and reactive phenolic resole resinin the presence of an acidic catalyst; b) combining the mixture formedin a) with expandable polystyrene particles; and c) conditioning themixture formed in b) to partially cure the reactive phenolic resoleresin.
 3. A process according to claim 2 wherein subsequent to formingthe mixture in a) said mixture is combined with expandable polystyreneparticles within 30 minutes when said mixture is at a temperature of 20°C.
 4. A process according to claim 1 wherein the conditioning isperformed at a temperature from between 50° C. and 75° C.
 5. A processaccording to claim 1 wherein the conditioning is performed for between0.25 and 10 hr.
 6. A process according to claim 1 wherein theconditioned mixture has a water content of less than 10% by weight basedon the total weight of the conditioned mixture and water.
 7. A processaccording to claim 1 wherein the expandable polystyrene particles arepartially expanded.
 8. A process according to claim 1 wherein thedensity of the expandable polystyrene particles is between 5 kg/m³ and20 kg/m³.
 9. A process according to claim 1 further comprising the stepof adding one or more fillers.
 10. A process according to claim 1wherein the filler is added in an amount of 0.5-60% by weight based onthe total weight of the composition.
 11. A process according to claim 1wherein the filler is a surface treated filler.
 12. A process accordingto claim 1 wherein the reactive phenolic resole resin has one or more ofthe following properties: (a) a viscosity between 500 and 4,000 cP; (b)a water content between 2 and 7% by weight; (c) a free phenol contentless than 25%; or (d) a free formaldehyde content of less than 3%.
 13. Aprocess according to claim 1 wherein the expandable thermoplasticmicrospheres have an average particle size from between 1 and 50 micronsand wherein the expandable microspheres contain a propellantencapsulated within a thermoplastic polymer shell.
 14. A processaccording to claim 13 wherein the thermoplastic polymer shell is derivedfrom monomers selected from the group consisting of acrylonitrile,methacrylonitrile, α-chloroacrylonitrile, α-ethoxyacrylonitrile,fumaroacrylonitrile, crotoacrylonitrile, acrylic esters, methacrylicesters, vinyl chloride, vinylidene chloride, vinylidene dichloride,vinyl pyridine, vinyl esters, and derivatives or mixtures thereof.
 15. Aprocess according to claim 1 wherein the acidic catalyst is selectedfrom a strong organic acid, an ester of a strong organic acid, a weakinorganic acid, an ester of a weak inorganic acid or mixtures thereof.16. A process for preparing a polystyrene foam composite comprising thesteps of: a) forming a mixture of expandable thermoplastic microspheres,reactive phenolic resole resin and expandable polystyrene particles inthe presence of an acidic catalyst; b) conditioning the mixture topartially cure the reactive phenolic resole resin; and c) further curingthe conditioned mixture with steam to form the composite.
 17. A processaccording to claim 16 comprising the steps of: a) forming a mixture ofexpandable thermoplastic microspheres and reactive phenolic resole resinin the presence of an acidic catalyst; b) combining the mixture formedin a) with expandable polystyrene particles to form a mixture; c)conditioning the mixture formed in b) to partially cure the reactivephenolic resole resin; and d) further curing the conditioned mixturewith steam to form the composite.
 18. A process according to claim 16wherein the conditioned mixture is held for between 4 and 48 hours priorto further curing.
 19. A process according to claim 16 wherein thefurther curing takes from between 1 minute and 60 minutes.
 20. A processaccording to claim 16 wherein the further curing is performed in a steamblock moulder, a sheet moulder or a continuous panel press.
 21. A foamcomposite produced by the process according to claim
 16. 22. A foamcomposite according to claim 21 wherein the specific mass loss rate @ 50kW, measured according to ISO 17554, is less than 8 g/m²·s.
 23. A foamcomposite according to claim 21 wherein the composite exhibits aninsulation failure time, according to AS1530.4, for a 100 mm thickpanel, of greater than 10 minutes.
 24. A composite block, panel or sheetfor use in construction comprising the foam composite according to claim21.